Chemiluminescent and smoke producing composition and method



United States Patent 3,551,343 CHEMILUMINESCENT AND SMOKE PRODUCING COMPOSITION AND METHOD Urho A. Lehikoinen, Detroit, Mich., assignor to Ethyl "Corporation, New York, N.Y., a corporation of Virginia No Drawing. Continuation-impart of application Ser. No. 561,418, June 29, 1966. This application Nov. 22, 1968,

Ser. No. 778,316

Int. Cl. B09k 3/00 US. Cl. 252-188.3 8 Claims ABSTRACT OF THE DISCLOSURE A chemiluminescent smoke composition which consists essentially of an aluminum alkyl, an ether which is free of acetylenic bonds, and a tetrakis(di-lower alkyl amino) ethylene. A method of producing a chemiluminescent smoke which comprises mixing said smoke composition with water.

CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of co-pending application Ser. No. 561,418, filed June 29, 1966, now abandoned.

SUMMARY OF THE INVENTION This invention pertains to chemiluminescent smokes containing an alkyl aluminum and a tetrakis(di-lower alkyl amino) ethylene. These smokes are visible by day and at night.

DESCRIPTION OF THE PREFERRED EMBODIMENTS An object of this invention, which is to prepare a night-visible smoke, is satisfied by providing a composition capable of generating a chemiluminescent smoke, said composition being prepared by (l) mixing an aluminum alkyl having the formula RRRA1 wherein R, R and R" are alkyl radicals of 1 to 4 carbon atoms, with 1 to 5 moles, per mole of said aluminum alkyl, of an ether having up to about carbon atoms and 1 to 3 ether-oxygen linkages, said ether being free of acetylenic bonds, and then (2) combining with the resultant mixture a tetrakis(dilower alkyl amino)ethylene, whereby the resulting mixture contains from 10 to 60 weight percent of said tetrakis(di-lower alkyl amino)ethylene.

These compositions yield chemiluminescent smoke clouds when admixed with water. The method of water mixing is not critical. The smoke agent may be injected underneath the surface of water to yield a cloud of chemiluminescent smoke above the surface of the water. Alternatively, the smoke agent can be merely admixed with water by shaking the agent and water in a vessel. Another method for contacting the agent with water is to introduce a stream of the agent into a water spray.

One essential ingredient in the smoke compositions of this invention is an aluminum compound of the types given above. Preferably, all alkyl radicals bonded to the aluminum atom are identical. Most preferably, these alkyl radicals are solely composed of carbon and hydrogen and have up to four carbon atoms. Typical exampels of alkyl aluminums which are applicable in this invention are trimethyl aluminum, triethyl aluminum, diethyl-aluminum hydride, methyl diethyl aluminum, triisopropyl aluminum, tri-sec-butyl aluminum, and the like.

3,551,343 Patented Dec. 29, 1970 wherein R and R are independently selected from alkyl groups having 1 to 4 carbon atoms; aryl groups such as phenyl and tolyl; alkenyl groups of 3-5 carbon atoms such as allyl; cycloalkyl groups such as cyclohexyl, and the like. Typically preferred ethers of this type are diethyl ether, isopropyl ether, allyl ether, phenyl ether, benzyl ether, benzyl ethyl ether, u-methylbenzyl ether, and the like. Cyclic monoethers can be employed. A highly preferred ether which is used in this invention is tetrahydrofuran. Biethers, that is, ethers which contain two ether-oxygen linkages, can be employed in this invention. Typical ethers of this type which may be employed are ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diamyl ether, and the like.

T riethers (sometimes referred to as tridentate ethers) which may be employed in this invention preferably have the ether oxygen linkages separated by two carbon atoms; that is, ethylene radicals. Typical ethers of this type which can be employed in this invention are diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

The alkyl aluminum and an ether above-described are simply mixed under anhydrous conditions and in the presence of an inert atmosphere. Typically, nitrogen is used to provide the inert atmosphere. However, other inert gases such as argon and neon can be employed, if desired. Best results are obtained when a chemiequivalent amount of the alkyl aluminum is admixed with an ether. When using a monoether, at least one mole of ether is employed for each mole of alkyl aluminum. Similarly, when a diether is employed, at least one-half mole of ether is employed for each mole of alkyl aluminum. Furthermore, with tn'dentate ethers the mole ratio of ether to aluminum is at least 1 to 3.

It is not necessary to employ an exactly chemiequivalent amount of ether and alkyl aluminum. An excess of ether can be used. When volatile ethers such as diethyl ether are employed, an excess of ether may be beneficial. In some instances, it appears that the presence of an excess of such an ether yields a larger smoke cloud. Consequently, it is convenient to employ up to five equivalents of ether for each equivalent of alkyl aluminum.

After the alkyl aluminum is mixed with the ether, it is then mixed with an amount of tetrakis(di-lower alkyl amino) ethylene which is sufficient to yield a final preparation containing from 10 to 60 weight percent of tetrakis compound. Again, mixing with the tetrakis compound is conveniently carried out using simple mixing procedures. A slight amount of heat may be beneficial, that is, it may be desirable to heat up the mixture to a temperature within the range of 3050 C. (For the purpose of this invention, lower alkyl signifies alkyl groups of 1 to 4 carbons.)

As pointed out above, the chemiluminescent smoke formulations of this invention yield smoke clouds which are visible at night when admixed with water. The water need not be pure; natural waters such as lake, river or sea water can be employed, as can muddy or wet earth. In addition, the water may be chemically-bound; that is, waters of hydration. When using chemically-bound water,

a compound which preferentially contains a large amount of waters of hydration is employed. Preferred compounds containing waters of hydration are alums. Typical alums which may be used are described on pages l96-l99 of the 8th edition of Langes Handbook of Chemistry, Handbook Publishers, Inc., Sandusky, Ohio (1952).

To further illustrate the invention, the following nonlimiting examples are presented. Unless otherwise indicated, all parts are by weight.

EXAMPLE 1 Two hundred and twenty-six milliliters of diethyl ether is admixed with 290 ml. of triethyl aluminum under anhydrous conditions and in the presence of a nitrogen atmosphere. To the resultant mixture is added 270 grams of tetrakis(dimethyl amino) ethylene.

The resultant smoke formulation yields a chemiluminescent smoke when admixed with water. For example, equal volumes of agent and water when admixed together yield a chemiluminescent smoke. Furthermore, such a smoke is produced when one volume of agent is injected under the surface of approximately 10 volumes of water without stirring. Thirdly, the formulation yields a chemiluminescent smoke when 50 parts of the formulation are added to 100 parts of [Ci- (SO -K SO -24H O].

EXAMPLE 2 Following the procedure of Example I, smoke formulations containing equimolar amounts of diethyl ether and triethyl aluminum and 40 percent of tetrakis(dimethyl amino)ethylene were prepared. When these formulations are admixed with water, chemiluminescent smokes were produced.

EXAMPLE 3 Equimolar amounts of tetrahydrofuran with triethyl aluminum and dioxane with triethyl aluminum were prepared using the procedure of Example 1. They were admixed With sufficient quantities of tetrakis(dimethyl amino)ethylene to yield formulations containing 20, 30, 40 and 50 weight percent of the tetrakis compound.

Results indicate that the best smokes are produced when the concentration of the tetrakis compound is from 30 to 40 Weight percent.

Following the procedure of Examples 1 and 3, smoke agents containing alkyl ether, phenyl ether, diethyl carbitol, anisole, p-chloroanisole, veratole, a-methylbenzyl ether and benzyl ether are prepared.

The smokes of this invention which are visible at night have many utilities. For example, they can be used for marking purposes in sea rescues. Similarly, they may be used to direct artillery fire or aerial bombardments.

An important aspect of this invention is that the smokes are visible by day and night. Hence, they have daytime and nighttime utilities. Accordingly, the compositions of this invention have a dual function. It is believed that this dual function is not accomplished by smokes and flares presently in use.

Having fully described the novel compositions of this invention, their method of preparation and their utility, it is desired that the scope of this invention be solely limited by the lawful extent of the appended claims.

What is claimed is:

1. A composition capable of generating chemiluminescent smoke, said composition being prepared by (l) mixing an aluminum alkyl having the formula:

RR'R"A1 wherein R, R and R are alkyl radicals of 1 to 4 carbon atoms, with l to 5 equivalents, per mole of said aluminum alkyl, of an ether having up to about 15 carbon atoms and 1 to 3 ether-Oxygen linkages, said ether being free of acetylenic bonds, and then (2) combining with the resultant mixture a tetrakis(dilower alkyl amino)ethylene, wherein the lower alkyl groups have 1 to 4 carbon atoms, whereby the resultant mixture contains from 10-60 weight percent of said tetrakis(di-lower alkyl amino)ethylene; said composition being prepared under substantially anhydrous conditions and in the presence of an inert atmosphere.

2. A composition of claim 1 wherein the aluminum alkyl is triethyl aluminum.

3. A composition of claim 2 wherein said tetrakis(dilower alkyl amino)ethylene is tetrakis(dimethylamino) ethylene.

4. A composition of claim 3 wherein said ether is diethyl ether.

5. A composition of claim 3 wherein said ether is tetrahydrofuran.

6. A composition of claim 3 wherein said ether is dioxane.

7. A method for producing a chemiluminescent smoke, said method comprising mixing a smoke composition of claim 1 with water.

8. A method of claim 7 wherein said water is from an alum having the formula [Cr (SO -K SO -24H O].

References Cited UNITED STATES PATENTS 3,309,268 3/1967 Sherman 42440 3,311,564 3/1967 Cline 252l88.3 3,400,082 9/1968 Gluckstein 252-305 JOHN DAVID WELSH, Primary Examiner US. Cl. X.R. 252-3 05 

